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EP0363769B1 - Process for preparing polytetrahydrofuran alkyl sulfonates and polytetrahydrofuran bisamines - Google Patents

Process for preparing polytetrahydrofuran alkyl sulfonates and polytetrahydrofuran bisamines Download PDF

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Publication number
EP0363769B1
EP0363769B1 EP89118185A EP89118185A EP0363769B1 EP 0363769 B1 EP0363769 B1 EP 0363769B1 EP 89118185 A EP89118185 A EP 89118185A EP 89118185 A EP89118185 A EP 89118185A EP 0363769 B1 EP0363769 B1 EP 0363769B1
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polytetrahydrofuran
formula
alkyl sulfonates
bisamines
preparing
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EP0363769A3 (en
EP0363769A2 (en
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Ulrich Dr. Koehler
Willibald Dr. Schoenleben
Hardo Dr. Siegel
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BASF SE
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/32—Polymers modified by chemical after-treatment
    • C08G65/329—Polymers modified by chemical after-treatment with organic compounds
    • C08G65/334—Polymers modified by chemical after-treatment with organic compounds containing sulfur
    • C08G65/3344—Polymers modified by chemical after-treatment with organic compounds containing sulfur containing oxygen in addition to sulfur
    • C08G65/3346—Polymers modified by chemical after-treatment with organic compounds containing sulfur containing oxygen in addition to sulfur having sulfur bound to carbon and oxygen

Definitions

  • This invention relates to a new process for the preparation of polytetrahydrofuran alkyl sulfonates by reacting polytetrahydrofuran with alkyl sulfonic acid halides and the use of the polytetrahydrofuran alkyl sulfonates thus prepared for the preparation of polytetrahydrofuran- ⁇ , ⁇ '-diamines.
  • polytetrahydrofuran- ⁇ , ⁇ '-diamines were of particular interest. Since the direct conversion of the terminal HO groups of the polytetrahydrofuran into amino groups gives a high proportion of secondary amines or hydrogenolysis of the polyether chains occurs (US Pat. No. 4,181,682), it has been proposed that the terminal HO groups of the polytetrahydrofuran initially be in to convert certain cationically active groups, and to convert the polytetrahydrofuran derivatives thus obtained to the corresponding ⁇ , ⁇ '-diamines. With this, e.g. processes described in US Pat. No.
  • 3,824,220 also start from the tetrahydrofuran itself.
  • the polymeric tetrahydrofuran with the desired cationically active end groups are out of the question for economical production. It is also unsatisfactory with regard to the purity of the products produced, since the formation of undesired by-products cannot be ruled out.
  • JP-A-70/16443 discloses a process in which polytetrahydrofuran-bis-p-toluenesulfonate is first prepared from polytetrahydrofuran by reaction with p-toluenesulfonic acid chloride, which is then aminated with ammonia.
  • the total yield given for the diamine is very low at 15.5%, and the work-up, which takes place via an ion exchange, is also complex.
  • US-A-3 405 105 describes the polymerization of tetrahydrofuran by reaction with an organic sulfonic acid, such as methanesulfonic acid.
  • organic sulfonic acid such as methanesulfonic acid.
  • the object was therefore to find a process which allows derivatives of polytetrahydrofuran to be obtained in a simple manner and with high uniformity to produce, which can be converted smoothly into the corresponding primary ⁇ , ⁇ '-amines.
  • polytetrahydrofuran alkyl sulfonates of the general formula are prepared in which R is an alkyl radical having 1 to 4 carbon atoms and n is an integer from 3 to 150, characterized in that polytetrahydrofuran of the general formula in which n has the meaning given above, with an alkylsulfonic acid halide of the general formula R-SO2-X III, in which x represents a chlorine, bromine or iodine atom and R has the meaning given above.
  • R denotes an alkyl radical having 1 to 4 carbon atoms, such as methyl, ethyl, propyl or butyl; n stands for an integer from 3 to 150, preferably 3 to 70, in particular 3 to 55. They are valuable intermediates for the production of polymer plastics.
  • the polytetrahydrofuran derivatives of the formula I are obtained by reacting tetrahydrofuran of the formula II with an alkylsulfonic acid halide of the formula III.
  • the alkylsulfonic acid halide is expediently used in the at least stoichiometric amount, for example up to twice the stoichiometric amount, based on the polytetrahydrofuran.
  • the excess is preferably up to 20%, in particular up to 10%.
  • the reaction is carried out at temperatures up to 100, preferably 0 to 70, in particular 10 to 40 ° C. and in the presence of basic substances.
  • Suitable basic substances are preferably tertiary amines, for example trialkylamines, such as tributylamine, triethylamine, N, N-dimethylaniline or heterocyclic nitrogen compounds with a tertiary N atom, such as pyridine, picoline and quinoline.
  • trialkylamines such as tributylamine, triethylamine, N, N-dimethylaniline or heterocyclic nitrogen compounds with a tertiary N atom, such as pyridine, picoline and quinoline.
  • One can act as basic Substances but also carbonates, hydroxides or hydrides of alkali or alkaline earth metals, such as potassium carbonate, potassium hydroxide, sodium hydride or alcoholates, such as potassium tertiary butoxylate.
  • the basic substances are used e.g. in stoichiometric amounts, based on the alkylsulfonic acid halide, but it is also possible to work with an excess or deficit of 10 to 20%.
  • the reaction is advantageously carried out in a solvent.
  • All solvents are suitable which do not react with the sulfonic acid halide under the reaction conditions and in which polytetrahydrofuran is soluble, e.g. Ethers such as methyl tert-butyl ether, diethyl ether, dioxane or tetrahydrofuran, carbonyl compounds such as acetone, methyl ethyl ketone, methyl isobutyl ketone or ethyl acetate, aliphatic hydrocarbons such as cyclohexane, methylene chloride or dichloroethane, or aromatic hydrocarbons such as toluene, benzene or xylene.
  • the reaction can also be carried out in the above-mentioned tertiary amines.
  • the implementation mixtures are easily e.g. worked up by adding water, separating the organic phase, washing with water to separate off the salts formed and, if appropriate, the solvent, and distilling off the remaining solvent.
  • the polytetrahydrofuran alkyl sulfonates of formula I can e.g. can be used for the production of bisamines of the formula IV.
  • the alkyl sulfonates are made by methods known per se, e.g. at temperatures from 0 to 100 ° C, in solvents, e.g.
  • Alcohols such as methanol, ethanol, isopropanol or butanol
  • ethers such as methyl tert-butyl ether, diethyl ether, dioxane, tetrahydrofuran, or aromatic hydrocarbons, such as toluene, benzene, xylene, or the above-mentioned tertiary amines are reacted with ammonia.
  • polytetrahydrofuran alkyl sulfonates achieved.
  • polytetrahydrofuran-bismethylsulfonate has unexpectedly more favorable properties, apparently because of the greater reactivity of the methylsulfonyl group compared to the toluenesulfonyl group.
  • the bismethanesulfonate of polytetrahydrofuran and methylsulfonic acid chloride is thus obtained at temperatures from 10 to 15 ° C. within 1 to 2 hours with 99% yields, based on the polytetrahydrofuran used.
  • Example 2 That after Polytetrahydrofuran-bismethylsulfonate obtained in Example 1 is spectroscopically pure and, when reacted with ammonia, gives the ⁇ , ⁇ '-diamine compound in yields of over 95%, the proportion of primary amine being from 95 to 99% (see Example 2) .
  • the analyzes show that almost exclusively polytetrahydrofuran chains with half-sided mesylated OH groups were formed.

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Description

Diese Erfindung betrifft ein neues Verfahren zur Herstellung von Polytetrahydrofuran-alkylsulfonaten durch Umsetzung von Polytetrahydrofuran mit Alkylsulfonsäurehalogeniden und die Verwendung der so hergestellten Polytetrahydrofuranalkylsulfonate für die Herstellung von Polytetrahydrofuran-ω,ω'-diaminen.This invention relates to a new process for the preparation of polytetrahydrofuran alkyl sulfonates by reacting polytetrahydrofuran with alkyl sulfonic acid halides and the use of the polytetrahydrofuran alkyl sulfonates thus prepared for the preparation of polytetrahydrofuran-ω, ω'-diamines.

Derivate des Polytetrahydrofurans sind gesuchte Zwischenprodukte für die Herstellung von Polymeren. Besonderes Interesse haben dabei Polytetrahydrofuran-ω,ω'-diamine gefunden. Da bei der direkten Überführung der endständigen HO-Gruppen des Polytetrahydrofurans in Aminogruppen ein hoher Anteil an sekundären Aminen erhalten wird oder Hydrogenolyse der Polyetherketten eintritt (US-A-4 181 682), hat man vorgeschlagen, die endständigen HO-Gruppen des Polytetrahydrofurans zunächst in bestimmte kationisch aktive Gruppen zu überführen, und die so erhaltenen Polytetrahydrofuranderivate zu den entsprechenden ω,ω'-Diaminen umzusetzen. Man kann bei diesem, z.B. in der US-A-3 824 220 beschriebenen Verfahren auch vom Tetrahydrofuran selbst ausgehen. In beiden Fällen wird, z.B. mit Hilfe von Trifluormethansulfonsäureanhydrid, das polymere Tetrahydrofuran mit den gewünschten kationisch aktiven Endgruppen erhalten. Für eine wirtschaftliche Herstellung kommt diese Methode nicht in Betracht. Sie ist auch hinsichtlich der Reinheit der hergestellten Produkte unbefriedigend, da sich die Bildung unerwünschter Nebenprodukte nicht ausschließen läßt.Derivatives of polytetrahydrofuran are sought-after intermediates for the production of polymers. Polytetrahydrofuran-ω, ω'-diamines were of particular interest. Since the direct conversion of the terminal HO groups of the polytetrahydrofuran into amino groups gives a high proportion of secondary amines or hydrogenolysis of the polyether chains occurs (US Pat. No. 4,181,682), it has been proposed that the terminal HO groups of the polytetrahydrofuran initially be in to convert certain cationically active groups, and to convert the polytetrahydrofuran derivatives thus obtained to the corresponding ω, ω'-diamines. With this, e.g. processes described in US Pat. No. 3,824,220 also start from the tetrahydrofuran itself. In both cases, e.g. with the help of trifluoromethanesulfonic anhydride, the polymeric tetrahydrofuran with the desired cationically active end groups. This method is out of the question for economical production. It is also unsatisfactory with regard to the purity of the products produced, since the formation of undesired by-products cannot be ruled out.

Aus der JP-A-70/16443 ist ein Verfahren bekannt, bei dem man aus Polytetrahydrofuran durch Umsetzung mit p-Toluolsulfonsäurechlorid zunächst Polytetrahydrofuran-bis-p-toluolsulfonat herstellt, das man dann mit Ammoniak aminiert. Die angegebene Gesamtausbeute für das Diamin ist mit 15,5 % sehr gering, auch ist die Aufarbeitung, die über einen Ionenaustausch erfolgt, aufwendig.JP-A-70/16443 discloses a process in which polytetrahydrofuran-bis-p-toluenesulfonate is first prepared from polytetrahydrofuran by reaction with p-toluenesulfonic acid chloride, which is then aminated with ammonia. The total yield given for the diamine is very low at 15.5%, and the work-up, which takes place via an ion exchange, is also complex.

In der US-A-3 405 105 wird die Polymerisation von Tetrahydrofuran durch Umsetzung mit einer organischen Sulfonsäure, wie Methansulfonsäure, beschrieben. Bei diesem Verfahren werden nach unseren Untersuchungen in geringer Ausbeute Polymerisate mit Molekulargewichten von etwa 1500 erhalten, die überwiegend nur halbseitig in Alkylsulfonatgruppen überführte HO-Gruppen enthalten.US-A-3 405 105 describes the polymerization of tetrahydrofuran by reaction with an organic sulfonic acid, such as methanesulfonic acid. In this process, according to our investigations, polymers with molecular weights of about 1500 are obtained in low yield, the majority of which contain HO groups which are only converted on one side into alkyl sulfonate groups.

Es bestand deshalb die Aufgabe, ein Verfahren zu finden, das es gestattet, Derivate des Polytetrahydrofurans auf einfache Weise und in hoher Einheitlichkeit herzustellen, die sich glatt in die entsprechenden primären ω,ω'-Amine überführen lassen.The object was therefore to find a process which allows derivatives of polytetrahydrofuran to be obtained in a simple manner and with high uniformity to produce, which can be converted smoothly into the corresponding primary ω, ω'-amines.

Nach dem neuen Verfahren, das diese Anforderungen in hohem Maße erfüllt, stellt man Polytetrahydrofuranalkylsulfonate der allgemeinen Formel

Figure imgb0001

in der R einen Alkylrest mit 1 bis 4 C-Atomen und n eine ganze Zahl von 3 bis 150 bedeuten, dadurch her, daß man Polytetrahydrofuran der allgemeinen Formel
Figure imgb0002
in der n die obengenannte Bedeutung hat, mit einem Alkylsulfonsäurehalogenid der allgemeinen Formel



        R-SO₂-X   III,



in der x ein Chlor-, Brom- oder Iodatom bedeutet und R die obengenannte Bedeutung hat, umsetzt.According to the new process, which fulfills these requirements to a high degree, polytetrahydrofuran alkyl sulfonates of the general formula are prepared
Figure imgb0001
in which R is an alkyl radical having 1 to 4 carbon atoms and n is an integer from 3 to 150, characterized in that polytetrahydrofuran of the general formula
Figure imgb0002
in which n has the meaning given above, with an alkylsulfonic acid halide of the general formula



R-SO₂-X III,



in which x represents a chlorine, bromine or iodine atom and R has the meaning given above.

In den Polytetrahydrofuranderivaten der Formel I bedeutet R einen Alkylrest mit 1 bis 4 C-Atomen, wie Methyl, Ethyl, Propyl oder Butyl; n steht für eine ganze Zahl von 3 bis 150, vorzugsweise 3 bis 70, insbesondere 3 bis 55. Sie sind wertvolle Zwischenprodukte für die Herstellung polymerer Kunststoffe.In the polytetrahydrofuran derivatives of the formula I, R denotes an alkyl radical having 1 to 4 carbon atoms, such as methyl, ethyl, propyl or butyl; n stands for an integer from 3 to 150, preferably 3 to 70, in particular 3 to 55. They are valuable intermediates for the production of polymer plastics.

Die Polytetrahydrofuranderivate der Formel I werden durch Umsetzung von Tetrahydrofuran der Formel II mit einem Alkylsulfonsäurehalogenid der Formel III erhalten. Das Alkylsulfonsäurehalogenid wird zweckmäßigerweise in der mindestens stöchiometrischen Menge, z.B. bis zur doppelten stöchiometrischen Menge, bezogen auf das Polytetrahydrofuran, eingesetzt.
Vorzugsweise beträgt der Überschuß bis zu 20 %, insbesondere bis zu 10 %. Man führt die Umsetzung bei Temperaturen bis 100, vorzugsweise 0 bis 70, insbesondere 10 bis 40°C und in Gegenwart von basisch wirkenden Stoffen durch. Als basisch wirkende Stoffe kommen vorzugsweise tertiäre Amine, z.B. Trialkylamine, wie Tributylamin, Triethylamin, N,N-Dimethylanilin oder heterocyclische Stickstoffverbindungen mit tertiärem N-Atom, wie Pyridin, Picolin und Chinolin in Betracht. Man kann als basisch wirkende Stoffe aber auch Carbonate, Hydroxide oder Hydride der Alkali- oder Erdalkalimetalle, wie Kaliumcarbonat, Kaliumhydroxid, Natriumhydrid oder Alkoholate, wie Kalium-tertiär-butoxylat einsetzen.The polytetrahydrofuran derivatives of the formula I are obtained by reacting tetrahydrofuran of the formula II with an alkylsulfonic acid halide of the formula III. The alkylsulfonic acid halide is expediently used in the at least stoichiometric amount, for example up to twice the stoichiometric amount, based on the polytetrahydrofuran.
The excess is preferably up to 20%, in particular up to 10%. The reaction is carried out at temperatures up to 100, preferably 0 to 70, in particular 10 to 40 ° C. and in the presence of basic substances. Suitable basic substances are preferably tertiary amines, for example trialkylamines, such as tributylamine, triethylamine, N, N-dimethylaniline or heterocyclic nitrogen compounds with a tertiary N atom, such as pyridine, picoline and quinoline. One can act as basic Substances but also carbonates, hydroxides or hydrides of alkali or alkaline earth metals, such as potassium carbonate, potassium hydroxide, sodium hydride or alcoholates, such as potassium tertiary butoxylate.

Man setzt die basisch wirkenden Stoffe z.B. in stöchiometrischen Mengen, bezogen auf das Alkylsulfonsäurehalogenid, ein, wobei jedoch auch mit einem Über- oder Unterschuß von 10 bis 20 % gearbeitet werden kann.The basic substances are used e.g. in stoichiometric amounts, based on the alkylsulfonic acid halide, but it is also possible to work with an excess or deficit of 10 to 20%.

Man führt die Umsetzung zweckmäßigerweise in einem Lösungsmittel durch. Geeignet sind alle Lösungsmittel, die unter den Umsetzungsbedingungen nicht mit dem Sulfonsäurehalogenid reagieren und in denen Polytetrahydrofuran löslich ist, das sind z.B. Ether, wie Methyl-tert.-butylether, Diethylether, Dioxan oder Tetrahydrofuran, Carbonylverbindungen, wie Aceton, Methylethylketon, Methylisobutylketon oder Essigester, aliphatische Kohlenwasserstoffe, wie Cyclohexan, Methylenchlorid oder Dichlorethan, oder aromatische Kohlenwasserstoffe, wie Toluol, Benzol oder Xylol. Man kann die Umsetzung aber auch in den obengenannten tertiären Aminen durchführen.The reaction is advantageously carried out in a solvent. All solvents are suitable which do not react with the sulfonic acid halide under the reaction conditions and in which polytetrahydrofuran is soluble, e.g. Ethers such as methyl tert-butyl ether, diethyl ether, dioxane or tetrahydrofuran, carbonyl compounds such as acetone, methyl ethyl ketone, methyl isobutyl ketone or ethyl acetate, aliphatic hydrocarbons such as cyclohexane, methylene chloride or dichloroethane, or aromatic hydrocarbons such as toluene, benzene or xylene. The reaction can also be carried out in the above-mentioned tertiary amines.

Die Umsetzungsgemische werden auf einfache Weise z.B. dadurch aufgearbeitet, daß man Wasser hinzugibt, die organische Phase abtrennt, zur Abtrennung gebildeter Salze und gegebenenfalls des Lösungsmittels mit Wasser wäscht und restliches Lösungsmittel abdestilliert.The implementation mixtures are easily e.g. worked up by adding water, separating the organic phase, washing with water to separate off the salts formed and, if appropriate, the solvent, and distilling off the remaining solvent.

Die Polytetrahydrofuran-alkylsulfonate der Formel I können z.B. für die Herstellung von Bisaminen der Formel IV verwendet werden. Zu diesem Zweck werden die Alkylsulfonate nach an sich bekannten Methoden, z.B. bei Temperaturen von 0 bis 100°C, in Lösungsmitteln, z.B. Alkoholen, wie Methanol, Ethanol, Isopropanol oder Butanol, Ethern, wie Methyl-tert.-butylether, Diethylether, Dioxan, Tetrahydrofuran, oder aromatischen Kohlenwasserstoffen, wie Toluol, Benzol, Xylol, oder den oben erwähnten tertiären Aminen mit Ammoniak umgesetzt.The polytetrahydrofuran alkyl sulfonates of formula I can e.g. can be used for the production of bisamines of the formula IV. For this purpose, the alkyl sulfonates are made by methods known per se, e.g. at temperatures from 0 to 100 ° C, in solvents, e.g. Alcohols, such as methanol, ethanol, isopropanol or butanol, ethers, such as methyl tert-butyl ether, diethyl ether, dioxane, tetrahydrofuran, or aromatic hydrocarbons, such as toluene, benzene, xylene, or the above-mentioned tertiary amines are reacted with ammonia.

Die Vorteile dieser Erfindung ergeben sich insbesondere aus der erzielten hohen Ausbeute und Reinheit der Polytetrahydrofuran-alkylsulfonate. Gegen- über über dem bekannten Polytetrahydrofuran-bis-p-toluolsulfonat weist das Polytetrahydrofuran-bismethylsulfonat, offensichtlich wegen der größeren Reaktivität der Methylsulfonylgruppe im Vergleich zu der Toluolsulfonylgruppe, unerwartet günstigere Eigenschaften auf. So erhält man das Bismethansulfonat aus Polytetrahydrofuran und Methylsulfonsäurechlorid schon bei Temperaturen von 10 bis 15°C innerhalb von 1 bis 2 Stunden mit 99 %iger Ausbeuten, bezogen auf eingesetztes Polytetrahydrofuran. Das nach Beispiel 1 erhaltene Polytetrahydrofuran-bismethylsulfonat ist spektroskopisch rein und liefert bei der Umsetzung mit Ammoniak die ω,ω'-Diamin-Verbindung in Ausbeuten von über 95 %, wobei der Anteil an primärem Amin bei 95 bis 99 % liegt (s. Beispiel 2).The advantages of this invention result in particular from the high yield and purity of the polytetrahydrofuran alkyl sulfonates achieved. Compared to the known polytetrahydrofuran-bis-p-toluenesulfonate, polytetrahydrofuran-bismethylsulfonate has unexpectedly more favorable properties, apparently because of the greater reactivity of the methylsulfonyl group compared to the toluenesulfonyl group. The bismethanesulfonate of polytetrahydrofuran and methylsulfonic acid chloride is thus obtained at temperatures from 10 to 15 ° C. within 1 to 2 hours with 99% yields, based on the polytetrahydrofuran used. That after Polytetrahydrofuran-bismethylsulfonate obtained in Example 1 is spectroscopically pure and, when reacted with ammonia, gives the ω, ω'-diamine compound in yields of over 95%, the proportion of primary amine being from 95 to 99% (see Example 2) .

Beispiel 1example 1 Herstellung von Polytetrahydrofuran-bismethylsulfonatProduction of polytetrahydrofuran bismethyl sulfonate

In einer mit Rückflußkühler, Tropftrichter und Innenthermometer versehenen 500 ml-Rührapparatur werden bei 10 bis 15°C 62,4 g Polytetrahydrofuran mit dem Molekulargewicht 624 (n = 6,4)(ca. 0,1 mol) in 170 ml Methyl-tert.-butylether (MTB) vorgelegt. Dann werden 24,3 g Triethylamin (0,24 mol) zugegeben. Danach tropft man unter gutem Rühren während ca. 1 Stunde 26,3 g Methansulfonsäurechlorid (0,23 mol) ein und hält das Reaktionsgemisch noch eine weitere Stunde bei 10 bis 15°C.In a 500 ml stirrer equipped with a reflux condenser, dropping funnel and internal thermometer, 62.4 g of polytetrahydrofuran with a molecular weight of 624 (n = 6.4) (approx. 0.1 mol) in 170 ml of methyl tert are at 10 to 15 ° C. .-Butyl ether (MTB) submitted. Then 24.3 g of triethylamine (0.24 mol) are added. 26.3 g of methanesulfonyl chloride (0.23 mol) are then added dropwise with thorough stirring and the reaction mixture is kept at 10 to 15 ° C. for a further hour.

Zur Abtrennung der gebildeten Ammoniumsalze wird das Reaktionsgemisch mit 400 ml Wasser versetzt. Die organische obere Phase wird zweimal mit je 100 ml gesättigter wäßriger NaCl-Lösung ausgeschüttelt. Nach dem Trocknen der organischen Phase wird das Lösungsmittel abdestilliert. Es bleiben 78,0 g (≙ ca. 0,1 mol, 100 % Ausbeute) Polytetrahydrofuran-bismethylsulfonat als farbloses, zähes Öl zurück.To separate the ammonium salts formed, 400 ml of water are added to the reaction mixture. The organic upper phase is extracted twice with 100 ml of saturated aqueous NaCl solution. After the organic phase has dried, the solvent is distilled off. 78.0 g ((approx. 0.1 mol, 100% yield) of polytetrahydrofuran-bismethylsulfonate remain as a colorless, viscous oil.

Analysen:Analyzes:

OH-Zahl: < 1
Säurezahl: < 1
Mol-Gewicht (osm.): 800
¹H-NMR (CDCl₃): 4.25 (t, α-CH₂), 3.4 (m, Polyether-CH₂), 3.0 (s, OCH₃), 1.85 (m, ß-CH₂), 1.63 (m, Polyether-CH₂).
IR (Film): 2940, 2857, 2798, 1356, 1176, 1111, 1021, 974, 943, 528 cm⁻¹.OH number: <1
Acid number: <1
Mol. Weight (osm.): 800
1 H-NMR (CDCl₃): 4.25 (t, α-CH₂), 3.4 (m, polyether-CH₂), 3.0 (s, OCH₃), 1.85 (m, ß-CH₂), 1.63 (m, polyether-CH₂).
IR (film): 2940, 2857, 2798, 1356, 1176, 1111, 1021, 974, 943, 528 cm -1.

Beispiel 2Example 2 Verwendung von Polytetrahydrofuran-bismethylsulfonat zur Herstellung von Polytetrahydrofuran-ω,ω'-diaminUse of polytetrahydrofuran-bismethylsulfonate for the production of polytetrahydrofuran-ω, ω'-diamine

In einem 300 ml Autoklav werden 11,2 g (≙ ca. 0,015 mol) nach Beispiel 1 erhaltenes Polytetrahydrofuran-bismethylsulfonat in 40 ml Methanol gelöst. Bei Raumtemperatur werden 65 ml Ammoniak zugepumpt. Man rührt 24 h unter Eigendruck (ca. 10 bar) und entspannt. Nach Zugabe von 100 ml 2 N Natronlauge wird dreimal mit 100 ml MTB ausgeschüttelt. Die vereinigten organischen Phasen werden getrocknet.11.2 g (≙ approx. 0.015 mol) of polytetrahydrofuran-bismethylsulfonate obtained according to Example 1 are dissolved in 40 ml of methanol in a 300 ml autoclave. 65 ml of ammonia are pumped in at room temperature. The mixture is stirred for 24 hours under autogenous pressure (approx. 10 bar) and relaxed. After adding 100 ml of 2N sodium hydroxide solution, the mixture is shaken out three times with 100 ml of MTB. The combined organic phases are dried.

Nach Abdestillieren des Lösungsmittels hinterbleiben 8,5 g Polytetrahydrofuran-ω,ω'-diamin (≙ 97.6 % Ausbeute) als zähes, farbloses Öl.After the solvent has been distilled off, 8.5 g of polytetrahydrofuran-ω, ω'-diamine (≙ 97.6% yield) remain as a viscous, colorless oil.

Analysen:Analyzes: Pot. Titration:Pot. Titration:

Primäres Amin: > 95 %
Sekundäres Amin: < 5 %
¹H-NMR (CDCl₃): 3.4 (m, Polyether-CH₂), 2.7 (t, α-CH₂), 1.62 (m, Polyether-CH₂), 1.43 (s, NH₂)
IR (Film): 2937, 2856, 2796, 1447, 1367, 1209, 1113, 984, 961, 735 cm⁻¹.Primary amine:> 95%
Secondary amine: <5%
1 H-NMR (CDCl₃): 3.4 (m, polyether-CH₂), 2.7 (t, α-CH₂), 1.62 (m, polyether-CH₂), 1.43 (s, NH₂)
IR (film): 2937, 2856, 2796, 1447, 1367, 1209, 1113, 984, 961, 735 cm -1.

Beispiel 3 (Vergleichsbeispiel gemäß Beispiel der US-A-3,405,105 mit Methansulfonsäure)Example 3 (Comparative Example According to Example US-A-3,405,105 with Methanesulfonic Acid)

Zu 360 g Tetrahydrofuran (5 mol) wurden unter Rühren bei Raumtemperatur 167 g Methansulfonsäure getropft (1,74 mol). Dann wurde das Gemisch weitere 5 h gerührt und auf 2 l Eiswasser gegeben. Dabei trat keine Phasentrennung auf. Daraufhin wurde dreimal mit je 100 ml MTB ausgeschüttelt. Die vereinigten organischen Phasen wurden getrocknet und im Wasserstrahlvakuum bei 50°C eingeengt. Es blieben 4,3 g eines öligen Rückstands zurück (≙ ca. 1 % Ausbeute bezogen auf Tetrahydrofuran).167 g of methanesulfonic acid (1.74 mol) were added dropwise to 360 g of tetrahydrofuran (5 mol) with stirring at room temperature. Then the mixture was stirred for a further 5 h and added to 2 l of ice water. No phase separation occurred. It was then shaken three times with 100 ml MTB each. The combined organic phases were dried and concentrated at 50 ° C. in a water jet vacuum. 4.3 g of an oily residue remained (≙ approx. 1% yield based on tetrahydrofuran).

Analysen:Analyzes:

Osm. Molgewicht: 1400 CHNOS-Analyse: gef.: 62,7 C 10,6 H - N 24,0 O 2,3 S theor.: 63,0 C 10,7 H - N 24,1 O 2,3 S
¹H-NMR (CDCl₃): 4,23 (t, -CH₂-O-SO₂-CH₃), 3,62 (t, -CH₂-OH), 3,4 (m, Polyether-CH₂), 3,0 (s, OCH₃), 2,6 (m, OH), 1,85 (m, -CH₂-CH₂-O-SO₂-CH₃), 1,63 (m, Polyether-CH₂)
Integrationsverhältnis -CH₂-O-SO₂-CH₃-Protonen zu -CH₂-OH-Protonen = 1:1.Osm. Molecular weight: 1400 CHNOS analysis: found: 62.7 C. 10.6 H. - N 24.0 O 2.3 p theor .: 63.0 C. 10.7 H. - N 24.1 O 2.3 p
1 H-NMR (CDCl₃): 4.23 (t, -C H ₂-O-SO₂-CH₃), 3.62 (t, -C H ₂-OH), 3.4 (m, polyether-CH₂), 3.0 (s, OC H ₃), 2.6 (m, OH), 1.85 (m, -C H ₂-CH₂-O-SO₂-CH₃), 1.63 (m, polyether-CH₂)
Integration ratio - C H₂-O-SO₂-CH₃ protons to -C H ₂-OH protons = 1: 1.

Die Analysen zeigen, daß praktisch ausschließlich Polytetrahydrofuran-Ketten mit halbseitig mesylierten OH-Gruppen entstanden sind.The analyzes show that almost exclusively polytetrahydrofuran chains with half-sided mesylated OH groups were formed.

Claims (3)

  1. A process for the preparation of a polytetrahydrofuran alkylsulfonate of the formula
    Figure imgb0007
     where R is alkyl of 1 to 4 carbon atoms and n is an integer of from 3 to 150, wherein a polytetrahydrofuran of the formula
    Figure imgb0008
     where n has the abovementioned meaning, is reacted with an alkylsulfonyl halide of the formula



            R-SO₂-X   III



    where X is chlorine, bromine or iodine and R has the abovementioned meaning.
  2. A process as claimed in claim 1, wherein the alkylsulfonyl halide is used in not less than the stoichiometric amount, based on the polytetrahydrofuran, and the reaction is carried out at up to 100°C in the presence of a basic substance.
  3. A process for the preparation of a bisamine of the formula
    Figure imgb0009
     where n has the meanings stated in claim 1, wherein a polytetrahydrofuran alkylsulfonate of the formula
    Figure imgb0010
     where n and R have the meanings stated in claim 1, which has been prepared by the process as claimed in claim 1, is reacted with ammonia at from 0 to 100°C.
EP89118185A 1988-10-08 1989-09-30 Process for preparing polytetrahydrofuran alkyl sulfonates and polytetrahydrofuran bisamines Expired - Lifetime EP0363769B1 (en)

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DE3834265 1988-10-08
DE3834265A DE3834265A1 (en) 1988-10-08 1988-10-08 METHOD FOR PRODUCING POLYTETRAHYDROFURANALKYL SULFONATES AND THE USE THEREOF

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3824219A (en) * 1963-06-24 1974-07-16 Minnesota Mining & Mfg Process for preparing polycationically active polymers of tetrahydrofuran
US3384681A (en) * 1964-12-02 1968-05-21 Asahi Chemical Ind Block copolymer prepared from amine terminated polyalkylene glycols and polyamides or polyureas
US3405105A (en) * 1965-11-12 1968-10-08 Phillips Petroleum Co Polymerization of tetrahydrofuran and derivatives thereof with organic sulfonic acids

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
Fieser and Fieser "Reagents for Organic Chemistry" p. 662, Wiley (1967) *
J. March "Advanced Organic Chemistry" 3rd Ed. p. 311-312, Wiley (1985); *
MAKROMOLEKULARE CHEMIE. RAPID COMMUNICATIONS,Nr. 7, Juli 1984; G. ZIEGAST et al.:" Linear and star-shaped hybrid polymers" *Seite 369-370* *

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DE58907283D1 (en) 1994-04-28
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EP0363769A2 (en) 1990-04-18
ES2061867T3 (en) 1994-12-16

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